Resonators are one of the most important parts of electronic products. They provide a stable reference frequency to ensure the operation of these products. Recently, the electronic products have the trend of miniaturization, which rendered the size reduction of the resonators as well [1]. Better design of the resonators relies on a better understanding of the crystals' nonlinear behavior [2]. The nonlinearities affect the quality factor and acoustic behavior of MEMS (Micro-Electro-Mechanical-System) and nano-structured resonators and filters [3]. Among these nonlinear effects, Drivel Level Dependence (DLD), which describes the instability of the resonator frequency due to voltage level and/or power density, is an urgent problem for miniaturized resonators [2]. Langasite and GaPO4 are new promising piezoelectric material. Resonators made from these new materials have superior performance such as good frequency-temperature characteristics, and low acoustic loss [2]. In this thesis, experimental measurements of drive level dependence of langasite resonators with different configurations (plano-plano, single bevel, and double bevel) are reported. The drive level dependence of GaPO4 resonators are reported as well for the purpose of comparison. The results show that the resonator configuration affects the DLD of the langasite resonator. Experiments for DLD at elevated temperature are also performed, and it was found that the temperature also affects the DLD of the langasite resonator.

Recently, the development of electronic technology towards higher frequencies and larger band widths has led to interest in finding new piezoelectric materials, which could be used to make filters with larger pass band widths and oscillators with better frequency stability. Langasite (La3Ga5SiO14, LGS) and its isomorphs have enticed considerable attention of researchers as a potential substrate material for piezoelectric device applications because of its high frequency stability and fairly good electromechanical coupling factors for acoustic wave devices. Nonlinear effect including drive level dependence, mode coupling, force-frequency effect and electroelasic effect are critical for the design of these devices. Third-order elastic constants (TOEC) play an important role in a quantitative analysis of these nonlinear effects. In particular these elastic constants are of great importance when the BAW (Bulk Acoustic Wave) and SAW (Surface Acoustic Wave) sensors of force, acceleration and so on are designed. Until now Langasite (LGS) and Langatate (LGT) crystal resonators have been qualified in terms of quality factor, temperature effect, isochronism defect and material quality. One of the most important advantages of those crystals is that they will not undergo phase transitions up to its melting temperature of 1450°. Presently there is no data on TOEC of LGT crystals. Our objective is to create an experimental procedure to measure and collect the complete set of third-order elastic constants of Langasite (La3Ga5SiO14) and Langatate (La3Ga5.5Ta0.5O14) crystals and compare the new values for langasite with values previously reported.

Ces travaux ont donc visé le développement d’une plateforme complète de détection de gaz pour environnement sévère haute température. Cette plateforme intègre un dispositif à ondes acoustiques de surface sur substrat Langasite, une résistance chauffante, une couche sensible inorganique nanostructurée et est placée dans une enceinte hermétique. Des températures de l’ordre de 450°C ont été atteintes et des tests de cyclages ont démontré un fonctionnement en accord avec les modèles théoriques et une reproductibilité des mesures. Des tests de détection de composés organiques volatils (éthanol et toluène) ont mis en avant des seuils de détection de l'ordre de quelques ppm. / Measuring pollutants concentrations in gas and vapors emissions are important environmental issues. This work presents a stand-alone portable device for high temperature assessment. The system includes a Langasite (LGS) acoustic sensor, a ceramic heater and a platform with RF connections for remote in-situ measurements. The packaging consists in a hermetic stainless steel cell which enables safe gas detection. In situ temperature measurements have been achieved and the thermal behavior was successfully investigated in the temperature range 25-450°C. The designed cell highlights good agreement with theoretical models and reproducibility of the measures. Volatile organic compounds exposures have been investigated and promising ppm level detections have been obtained.

The langasites are a class of geometrically frustrated compounds with the formula A3XY3Z2O14 where A,X,Y,Z are cationic sites and site A is occupied by a magnetic ion. The interactions of the magnetic ions form a star shaped pattern called the Kagomé lattice. The langasites have been widely studied by the solid state community because of their functional properties such as piezoelectricity, multiferroicity, ferroelectricity, dielectricity and for use in the telecommunication industry. It was also realized that some langasite materials exhibit exotic magnetic ground states at low temperatures. A thorough understanding of their ground state is limited by the difficulty in synthesizing new members belonging to this series due to the formation of competing phases such as the garnets. In this study, four new magnetic langasites A3Ga3Ge2BeO14 (A= Pr, Nd, Sm and Eu) and a non-magnetic lattice standard La3Ga3Ge2BeO14 were synthesized. These were further structurally characterized by powder X-ray diffraction, Rietveld refinement and bond valence analysis. Further characterization of the low-temperature magnetism was done by performing magnetization, magnetic susceptibility (field cooled and zero field cooled) and heat capacity measurements. The low temperature spin dynamics were probed using muon spin resonance performed at TRIUMF (Vancouver) and elastic and inelastic neutron scattering measurements performed at the DCS (NIST) and D7 (ILL). From all the above measurements it can be concluded that the new Be langasites exhibit net antiferromagnetic interactions at low-temperatures with clear signs of diffuse scattering for Nd3Ga3Ge2BeO14 using inelastic neutron scattering measurements. There was no evidence of magnetic long-range ordering down to as low as 0.025 K. Based on the obtained measurements these new Be-langasite compounds can be classified as potential spin liquid candidates. / February 2017

Éléments essentiels des systèmes de télécommunication depuis environ trente ans, les dispositifs à ondes élastiques de surface offrent également l'opportunité, de par leur sensibilité aux conditions environnementales et leur caractère passif, de réaliser des capteurs sans-fil autonomes (sans électronique ni source d'énergie embarquées), configuration particulièrement intéressante pour la mesure à haute température. Nos travaux se sont focalisés sur le choix des matériaux pouvant constituer de tels capteurs, au niveau des deux éléments les constituant : le substrat piézoélectrique et les électrodes métalliques. Ces dernières sont généralement constituées de platine, de par l'inertie chimique particulièrement importante de ce métal noble. Nos travaux nous ont permis d'attribuer la dégradation de ces électrodes, généralement observée aux alentours de 700°C, à un phénomène spécifique des films minces, dénommé agglomération, nous conduisant par la suite à envisager et à tester des solutions plus efficaces. En ce qui concerne le substrat, nos efforts ont porté sur la structure bicouche AlN/Saphir, prometteuse pour de telles applications, mais encore peu étudiée. Après l'optimisation des paramètres de dépôt du film mince par pulvérisation réactive magnétron, permettant d'obtenir une couche épitaxiée, nous nous sommes intéressés à la résistance à l'oxydation de l'AlN à haute température dans l'air. L'utilisation croisée de la diffraction des rayons X, de l'ellipsométrie et de la spectroscopie de masse des ions secondaires nous a permis de montrer que l'on peut envisager l'emploi de cette structure bicouche pour les applications visées à des températures allant jusqu'à 700°C / Surface acoustic waves devices are key components of telecommunication systems for more than thirty years or so. Because they are passive and very sensitive to external conditions, they also offer the possibility to make autonomous wireless sensors (electronic-less and battery-less), which could be particularly interesting in high-temperature environments. Our work was focused on the choice of materials allowing the fabrication of such sensors for both parts of the device: piezoelectric substrate and metallic electrodes. The latter are generally made of platinum because of the great chemical inertness of this noble metal. Our work allowed us to attribute their degradation, starting around 700°C on, to a phenomenon called agglomeration which is very specific to thin films. This result led us to consider and test more efficient solutions. Regarding the substrate, we mainly studied AlN/Sapphire bilayer structure, promising for such applications but not really studied yet. After the optimization of the deposition parameters of the thin film, realized by reactive magnetron sputtering, leading to the epitaxial quality, we studied the strength of AlN to oxidation under high temperature in air atmosphere. Results given by X-ray diffraction, ellipsometry and secondary ion mass spectroscopy converged to show that AlN/Sapphire structure is a good candidate for such applications at temperatures up to 700°C

In this study, gas sensing systems that are based on piezoelectric smart material and structures are proposed, designed, developed, and tested, which are mainly aimed to address the temperature dependent CO2 gas sensing in a real environment. The state-of-the-art of gas sensing technologies are firstly reviewed and discussed for their pros and cons. The adsorption mechanisms including physisorption and chemisorption are subsequently investigated to characterize and provide solutions to various gas sensors. Particularly, a QCM based gas sensor and a C-axis inclined zigzag ZnO FBAR gas sensor are designed and analyzed for their performance on room temperature CO2 gas sensing, which fall into the scope of physisorption. In contrast, a Langasite (LGS) surface acoustic wave (SAW) based acetone vapor sensor is designed, developed, and tested, which is based on the chemisorption analysis of the LGS substrate. Moreover, solid state gas sensors are characterized and analyzed for chemisorption-based sensitive sensing thin film development, which can be further applied to piezoelectric-based gas sensors (i.e. Ca doped ZnO LGS SAW gas sensors) for performance enhanced CO2 gas sensing. Additionally, an innovative MEMS micro cantilever beam is proposed based on the LGS nanofabrication, which can be potentially applied for gas sensing, when combined with ZnO nanorods deposition. Principal component analysis (PCA) is employed for cross-sensitivity analysis, by which high temperature gas sensing in a real environment can be achieved. The proposed gas sensing systems are designated to work in a high temperature environment by taking advantage of the high temperature stability of the piezoelectric substrates.

Piezoelectric materials are well known for their applications in surface (SAW) and bulk acoustic wave (BAW) devices such as oscillators, resonators and sensors. Quartz has been the main material used in such applications. Ternary calcium gallium germanate (CGG) structure-type materials, so-called langasites, recently emerged as very promising because of their piezoelectric properties superior to quartz. This thesis discusses the growth of langasite-type La3Ga5.5Ta0.5O14 (LGT) films by liquid phase epitaxy (LPE) technique and their chemical and structural characterization. In addition, the different techniques suitable for the growth of LGT are discussed and compared. To adjust the materials properties for given applications, doping by selected ions can be used. However, the dopants must be homogeneously distributed. In the current study, Al, Ti, Cr and Ca were investigated as dopants. In an earlier study, Al and Ti had been chosen because of their ability to substitute the octahedral site of LGT, normally occupied by Ga (CN=VI) with a segregation coefficient near unity in Czochralski growth. Doping with Ca and Cr has never been reported before, and therefore, the segregation behavior was unknown. In this study, Al, Ti and co-doping with Cr and Ca has been investigated for both X and Y-oriented films. The dopant distribution in the films was quantitatively evaluated by Secondary Ion Mass Spectroscopy (SIMS), using ion-implanted LGT substrates as standards. The drop of dopant concentration, in the SIMS profile, allows for the identification of the film-substrate interface and to accurately measure the thickness of the films. The film thickness is found to be typically of the order 0.5 to 2µm, depending on growth conditions. The solvent was found a reliable choice, as solvent ions were not incorporated in the films above the detection limits of the characterization techniques. A lead oxide solvent system is used as a solvent for the growth of LGT LPE films with different orientations. Extensive structural characterization was performed. The crystallinity of substrates and films grown with different orientations was compared by X-ray diffraction (XRD). The films show a very high structural perfection, with typically FWHM values of 0.035 for the (004) reflection of the XRD rocking curve. The films were also characterized by TEM. The optical transmittance of the films was characterized by Varian optical spectrophotometer, and the value obtained of approximately 80% is comparable with the transmittance value of the Czochralski grown polished substrate.

No description available.

Ces travaux ont visé le développement d'une plateforme complète de détection de gaz pour environnement sévère haute température. Cette plateforme intègre un dispositif à ondes acoustiques de surface sur substrat Langasite, une résistance chauffante, une couche sensible inorganique nanostructurée et est placée dans une enceinte hermétique. Des températures de l'ordre de 450 °C ont été atteintes et des tests de cyclages ont démontré un fonctionnement reproductible en accord avec les modèles théoriques. Des tests de détection de composés organiques volatils (éthanol et toluène) ont mis en avant le fort potentiel du couplage entre dispositifs acoustiques et couches sensibles mésoporeuses présentant des seuils de détection de l'ordre de quelques ppm.

Ces études ont pour objectif la mise en œuvre de bi-matériaux constitués d'une phase catalytique active vis-à-vis de divers gaz (méthane), et d'une phase ferroélectrique-piézoélectrique sensible aux modifications de la phase catalytique (ou absorbante). Les phases catalytiques de base sont le dioxyde de cérium CeO2 et le cérate de baryum BaCeO3. Le système « oxyde de lanthane-hydroxycarbonate » La2O3 - La(OH)x (CO3)y a de même été étudié comme phase catalytique potentielle : son intérêt réside dans sa composition, variable en fonction de la température de travail. La phase piézoélectrique choisie est la langasite La3Ga5SiO14 qui présente l'avantage de rester piézoélectrique au-dessus de 1000°C, et peut donc être utilisée dans des systèmes catalytiques à des températures élevées (600°C). Dans une première partie nous présentons une étude bibliographique des enjeux environnementaux de la réalisation de nouveaux capteurs de gaz, notamment fonctionnant selon le principe de perturbation d'ondes acoustiques de surface. Une revue des travaux existants est développée. Les diverses techniques utilisées sont rassemblées dans un chapitre spécifique (méthodes de synthèses, diffraction de rayons X, spectroscopie infrarouge, microscopies électroniques, mesures électriques) .Les synthèses et caractérisations des phases (CeO2, BaCeO3, La2O3 ...) développées en tant que phases catalytiques optimisées sont détaillées dans une première étape. Certaines phases ont été obtenues sous des formes nanostructurées, performantes d'un point de vue conversion de CH4 en CO2. Les comportements lors de décompositions thermiques de l'hydroxycarbonate de lanthane ont été étudiés par analyses thermiques, spectroscopie infrarouge et mesures d'impédances électriques. La phase piézoélectrique La3Ga5SiO14 (langasite) a été synthétisée selon diverses approches nouvelles (réaction solide, sol-gel) : la synthèse est difficile, car, selon divers auteurs, ce composé est caractérisé par une fusion incongruente. La phase polycristalline obtenue après divers cycles thermiques atteint en fait une haute pureté apparente. La vérification de la qualité cristalline a été réalisée par un affinement structural (Rietveld) qui a permis de confirmer la qualité de la phase obtenue. Les coordonnées atomiques affinées à partir de diagrammes de diffraction de rayons X sont très proches de celles figurant dans la littérature pour un monocristal. Des études par spectroscopie IRTF et mesures électriques ont de même été réalisées. Enfin des couches minces de langasite, de lanthane et d'oxycarbonate de lanthane ont été obtenues à partir de voies sol-gel suivies de dépôt par spin-coating (et cela pour la première fois). Des bicouches langasite/lanthane sur substrat silicium ont été obtenues avec une bonne cohésion d'ensemble. Ces premières bicouches feront l'objet d'études ultérieures approfondies